TW202307570A - Photosensitive resin composition and use thereof, display device, semiconductor device which is specially composed of an oxime ester compound and has good film-forming properties - Google Patents

Abstract

A photosensitive resin composition comprises an alkali-soluble resin, a polymerizable monomer different from the alkali-soluble resin, and at least one photoinitiator of an oxime ester compound represented by formula I. The oxime ester compound represented by the formula I has high thermal stability, has good solubility to solvents generally used for preparing photosensitive resin compositions, and can also make the photosensitive resin composition have good film-forming properties, developing properties and photosensitivity. The photosensitive resin composition is suitable for use in preparing photocurable materials such as semiconductor photoresists, colored photoresists, and photo spacers.

Description

Photosensitive resin composition and use thereof, display device, semiconductor device

The present invention relates to a photosensitive resin composition, in particular to a photosensitive resin composition containing oxime ester compounds and its application.

Oxime ester compounds are widely used as photoinitiators due to their excellent photosensitive properties and are used in the photocuring of optoelectronic components such as RGB color photoresist, black matrix photoresist, photo spacer, and semiconductor photoresist. Material.

其中，R ¹至R ¹¹各自獨立地代表氫原子、鹵素原子、經取代或未經取代之碳數為1至20之烷基、經取代或未經取代之碳數為2至20之烯基、經取代或未經取代之形成環之原子數為3至10之環烷基、經取代或未經取代之碳數為4至20之環烯基、羥基、經取代或未經取代之碳數為1至20之烷氧基、經取代或未經取代之碳數為2至20之烯氧基、經取代或未經取代之碳數為1至20之烷醯基、經取代或未經取代之碳數為2至20之烯醯基、經取代或未經取代之形成環之碳數為6至14之芳基或經取代或未經取代之形成環之原子數為3至14之雜環基；Ar代表經取代或未經取代之形成環之碳數為6至14之芳基或經取代或未經取代之形成環之原子數為5至14之雜芳基；W是代表單鍵或氧原子；Z是代表單鍵、氧原子或＞NR ^3’(R ^3’代表經取代或未經取代之碳數為1至20之烷基，或R ^3’是與R ³連接而與氮原子一起形成環)。 The Republic of China patent publication TW 201140240A discloses a photopolymerization initiator represented by the following general formula:

Among them, ^R1 to ^R11 each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group with a carbon number of 1 to 20, a substituted or unsubstituted alkenyl group with a carbon number of 2 to 20 , substituted or unsubstituted cycloalkyl with 3 to 10 atoms forming the ring, substituted or unsubstituted cycloalkenyl with 4 to 20 carbons, hydroxyl, substituted or unsubstituted carbon Alkoxy with 1 to 20 carbons, substituted or unsubstituted alkenyloxy with 2 to 20 carbons, substituted or unsubstituted alkyl with 1 to 20 carbons, substituted or unsubstituted A substituted or unsubstituted alkenyl group with 2 to 20 carbon atoms, a substituted or unsubstituted aryl group with 6 to 14 carbon atoms forming a ring, or a substituted or unsubstituted ring with 3 to 14 atoms Ar represents a substituted or unsubstituted aryl group with 6 to 14 ring carbon atoms or a substituted or unsubstituted heteroaryl group with 5 to 14 ring atoms; W is Represents a single bond or an oxygen atom; Z represents a single bond, an oxygen atom, or >NR ^3' (R ^3' represents a substituted or unsubstituted alkyl group with a carbon number of 1 to 20, or R ^3' is a combination with R ³ linked to form a ring with the nitrogen atom).

With the increasing demand for properties of various optoelectronic components, the solubility and thermal stability of oxime ester compounds as photoinitiators, and the film-forming properties, developability, and sensitivity of photosensitive resin compositions containing oxime ester compounds The requirements for such properties are also increased, so the oxime ester compounds still need to be further improved to meet the subsequent application requirements of various optoelectronic components.

Therefore, the first object of the present invention is to provide a photosensitive resin composition.

該式I中，R ¹至R ⁴各自獨立地表示C ₁至C ₂₀直鏈烷基、C ₃至C ₂₀支鏈烷基、C ₂至C ₂₀直鏈烯基、C ₄至C ₂₀支鏈烯基、環烷基或芳香基，其中，該環烷基及該芳香基為未經取代或所含的任一個氫原子被前述烷基或烯基取代， R ⁵表示氫、鹵素、硝基、氰基、C ₁至C ₂₀直鏈烷基、C ₃至C ₂₀支鏈烷基、環烷基或芳香基，其中，該環烷基及該芳香基為未經取代或所含的任一個氫原子被前述烷基取代， R ⁶表示氫、C ₁至C ₂₀直鏈烷基、C ₃至C ₂₀支鏈烷基、C ₂至C ₂₀直鏈烯基、C ₄至C ₂₀支鏈烯基、環烷基或芳香基，其中，該環烷基及該芳香基為未經取代或所含的任一個氫原子被前述烷基或烯基取代， 上述R ¹至R ⁶表示的基團中所含的任一個−CH ₂−為未經取代或被一個由下列所構成群組之取代基所取代：−O−、−S−、−NH−、−C=O−、−O(C=O)−、−(C=O)O−、−NH(C=O)−及−(C=O)NH−，且相鄰的−CH ₂−不可以同時被上述取代基所取代，及 R ⁷表示橋環基或具橋環基的衍生物。 Thus, the photosensitive resin composition of the present invention includes: an alkali-soluble resin; a polymerizable monomer different from the alkali-soluble resin; and a photoinitiator, including at least one oxime ester compound represented by formula I: [Formula I]

In this formula I, R ¹ to R ⁴ each independently represent C ₁ to C ₂₀ straight chain alkyl, C ₃ to C ₂₀ branched chain alkyl, C ₂ to C ₂₀ straight chain alkenyl, C ₄ to C ₂₀ branched Alkenyl, cycloalkyl or aryl, wherein, the cycloalkyl and the aryl are unsubstituted or any hydrogen atom contained is substituted by the aforementioned alkyl or alkenyl, R ⁵ represents hydrogen, halogen, nitrate group, cyano group, C ₁ to C ₂₀ linear alkyl group, C ₃ to C ₂₀ branched chain alkyl group, cycloalkyl group or aryl group, wherein the cycloalkyl group and the aryl group are unsubstituted or contained Any hydrogen atom is substituted by the aforementioned alkyl group, R ⁶ represents hydrogen, C ₁ to C ₂₀ straight chain alkyl, C ₃ to C ₂₀ branched chain alkyl, C ₂ to C ₂₀ straight chain alkenyl, C ₄ to C ₂₀ Branched alkenyl, cycloalkyl or aryl, wherein, the cycloalkyl and aryl are unsubstituted or any hydrogen atom contained is substituted by the aforementioned alkyl or alkenyl, the above R ¹ to R ⁶ represent Any −CH ₂ − contained in the group is unsubstituted or substituted by a substituent consisting of the following groups: −O−, −S−, −NH−, −C=O−, −O(C=O)−, −(C=O)O−, −NH(C=O)− and −(C=O)NH−, and adjacent −CH ₂ − cannot be replaced by the above at the same time Substituted by a group, and R ⁷ represents a bridged ring group or a derivative of a bridged ring group.

Therefore, the second object of the present invention is to provide an oxime ester compound.

該式I中，R ¹至R ⁴各自獨立地表示C ₁至C ₂₀直鏈烷基、C ₃至C ₂₀支鏈烷基、C ₂至C ₂₀直鏈烯基、C ₄至C ₂₀支鏈烯基、環烷基或芳香基，其中，該環烷基及該芳香基為未經取代或所含的任一個氫原子被前述烷基或烯基取代； R ⁵表示氫、鹵素、硝基、氰基、C ₁至C ₂₀直鏈烷基、C ₃至C ₂₀支鏈烷基、環烷基或芳香基，其中，該環烷基及該芳香基為未經取代或所含的任一個氫原子被前述烷基取代； R ⁶表示氫、C ₁至C ₂₀直鏈烷基、C ₃至C ₂₀支鏈烷基、C ₂至C ₂₀直鏈烯基、C ₄至C ₂₀支鏈烯基、環烷基或芳香基，其中，該環烷基及該芳香基為未經取代或所含的任一個氫原子被前述烷基或烯基取代； 上述R ¹至R ⁶表示的基團中所含的任一個−CH ₂−為未經取代或被一個由下列所構成群組之取代基所取代：−O−、−S−、−NH−、−C=O−、−O(C=O)−、−(C=O)O−、−NH(C=O)−及−(C=O)NH−，且相鄰的−CH ₂−不可以同時被上述取代基所取代；及 R ⁷表示橋環基或具橋環基的衍生物。 Thus, the oxime ester compound of the present invention is represented by formula I: [Formula I]

In this formula I, R ¹ to R ⁴ each independently represent C ₁ to C ₂₀ straight chain alkyl, C ₃ to C ₂₀ branched chain alkyl, C ₂ to C ₂₀ straight chain alkenyl, C ₄ to C ₂₀ branched Alkenyl, cycloalkyl or aryl, wherein, the cycloalkyl and the aryl are unsubstituted or any hydrogen atom contained is substituted by the aforementioned alkyl or alkenyl; ^R represents hydrogen, halogen, nitro group, cyano group, C ₁ to C ₂₀ linear alkyl group, C ₃ to C ₂₀ branched chain alkyl group, cycloalkyl group or aryl group, wherein the cycloalkyl group and the aryl group are unsubstituted or contained Any hydrogen atom is replaced by the aforementioned alkyl group; R ⁶ represents hydrogen, C ₁ to C ₂₀ straight chain alkyl, C ₃ to C ₂₀ branched chain alkyl, C ₂ to C ₂₀ straight chain alkenyl, C ₄ to C ₂₀ Branched alkenyl, cycloalkyl or aryl, wherein, the cycloalkyl and aryl are unsubstituted or any hydrogen atom contained is substituted by the aforementioned alkyl or alkenyl; the above R ¹ to R ⁶ represent Any −CH ₂ − contained in the group is unsubstituted or substituted by a substituent consisting of the following groups: −O−, −S−, −NH−, −C=O−, −O(C=O)−, −(C=O)O−, −NH(C=O)− and −(C=O)NH−, and adjacent −CH ₂ − cannot be replaced by the above at the same time Substituted by a group; and R ⁷ represents a bridged ring group or a derivative of a bridged ring group.

Therefore, the third object of the present invention is to provide an application of the above-mentioned photosensitive resin composition.

Therefore, the application of the above-mentioned photosensitive resin composition of the present invention includes the application in the preparation of photo-spacers, colored photoresists or photoresists for semiconductors.

Therefore, the fourth object of the present invention is to provide a display device.

Therefore, the display device of the present invention includes a colored photoresist formed of the above-mentioned photosensitive resin composition.

Therefore, the fifth object of the present invention is to provide a semiconductor device.

Therefore, the semiconductor device of the present invention includes a photoresist for a semiconductor formed of the above-mentioned photosensitive resin composition.

The effect of the present invention is that: the molecular structure of the oxime ester compound of the present invention comprises a carbazole (carbazole) group as the main skeleton, two substituents comprising an oxime ester group, and a bridged ring group or a derivative with a bridged ring group, The oxime ester compound has high thermal stability and good solubility in solvents generally used to prepare photosensitive resin compositions, so it is particularly suitable as a photoinitiator for photosensitive resin compositions.

Another effect of the present invention is that: the photosensitive resin composition containing the above-mentioned oxime ester compound has high photosensitivity, and is suitable for use in the preparation of light-curing materials such as semiconductor photoresists, colored photoresists, and photo-spacers. It is especially suitable for the preparation of black matrix photoresist, and the photosensitive resin composition has good film-forming and developing properties, which can avoid mura defects in the display device. In addition, because the oxime ester compound has high thermal stability properties so that the photosensitive resin composition has good thermal stability.

The term "(meth)acrylate" herein generally refers to methacrylate and/or acrylate.

The photosensitive resin composition of the present invention includes an alkali-soluble resin, a polymerizable monomer and a photoinitiator.

The type of the alkali-soluble resin is not particularly limited, it can be any alkali-soluble resin known in the technical field of photocurable materials, and for those who are familiar with the technical field of photocurable materials, it can be based on the follow-up practice of the photosensitive resin composition. Application and flexible selection. In some embodiments of the present invention, the alkali-soluble resin is selected from (meth)acrylate resins, novolac resins, epoxy resins, polyvinylphenol resins, and carboxyl-containing urethane One or more of ester resins. Wherein, the (meth)acrylate resin is such as but not limited to carboxyl-containing (meth)acrylate resin, hydroxyl-containing (meth)acrylate resin, and epoxy-containing (meth)acrylic acid One or more of ester resins. The novolak-based resin is, for example, but not limited to carboxyl-containing novolak-based resin. The epoxy resin is, for example but not limited to, carboxyl-containing epoxy resin. Preferably, the solid content of the photosensitive resin composition is 100% by weight, and the content of the alkali-soluble resin is in the range of 5% to 60% by weight, so that the photosensitive resin composition has better developability ; More preferably, the content of the alkali-soluble resin ranges from 10% to 50% by weight; most preferably, the content of the alkali-soluble resin ranges from 12% to 30% by weight.

The polymerizable monomer is different from the alkali-soluble resin, the type of the polymerizable monomer is not particularly limited, it can be any polymerizable monomer known in the technical field of photocurable materials, and it is a person who is familiar with the technical field of photocurable materials Personnel can choose flexibly according to the subsequent practical application of the photosensitive resin composition. In some embodiments of the present invention, the polymerizable monomer is selected from epoxy-containing polymerizable monomers, polymerizable monomers containing at least one ethylenically unsaturated bond, and epoxy- and vinyl-containing One or more of polymerizable monomers with unsaturated bonds. Wherein, the epoxy group-containing polymerizable monomer is, for example but not limited to, epoxy bisphenol fluorene, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexyl carboxylate and the like. The polymerizable monomers containing epoxy groups and ethylenically unsaturated bonds are such as but not limited to ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate , Diglycidyl phthalate di(meth)acrylate, glycerol polyglycidyl ether poly(meth)acrylate, 1,2-epoxy-4-vinylcyclohexane, etc. The polymerizable monomer containing at least one ethylenically unsaturated bond is one or more selected from compounds containing one vinyl group and compounds containing two or more vinyl groups. The compound containing one vinyl group is for example but not limited to (meth)acrylate compound, (meth)acrylamide compound or hydroxyl (meth)acrylate compound. The compound containing more than two vinyl groups is for example but not limited to tripropylene glycol diacrylate (tripropylene glycol diacrylate, TPGDA), trimethylolpropane triacrylate (trimethylolpropane triacrylate, TMPTA), pentaerythritol triacrylate (pentaerythritol triacrylate) , PETA) or dipentaerythritol hexaacrylate (di-pentaerythritol hexaacrylate, DPHA), etc. Preferably, taking the solid content of the photosensitive resin composition as 100% by weight, the content of the polymerizable monomer ranges from 5% to 60% by weight, which can make the photosensitive resin composition have better curing properties; more preferably, the content range of the polymerizable monomer is 10% by weight to 50% by weight; most preferably, the content range of the polymerizable monomer is 12% by weight to 30% by weight.

。 The photoinitiator includes at least one oxime ester compound represented by formula I: [Formula I]

.

In this formula I, R ¹ to R ⁴ each independently represent C ₁ to C ₂₀ straight chain alkyl, C ₃ to C ₂₀ branched chain alkyl, C ₂ to C ₂₀ straight chain alkenyl, C ₄ to C ₂₀ branched Alkenyl, cycloalkyl or aryl, wherein, the cycloalkyl and the aryl are unsubstituted or any hydrogen atom contained is replaced by the aforementioned straight-chain alkyl, branched-chain alkyl, straight-chain alkenyl or Branched alkenyl substitution. Preferably, the R ¹ to R ⁴ each independently represent a C ₁ to C ₈ linear alkyl group, a C ₃ to C ₁₀ branched chain alkyl group or a C ₃ to C ₆ cycloalkyl group. More preferably, R ¹ and R ² each independently represent a C ₁ to C ₂ straight chain alkyl group, R ³ and R ⁴ each independently represent a C ₁ to C ₅ straight chain alkyl group or a C ₃ to C ₁₀ branched chain alkane base.

R ⁵ represents hydrogen, halogen, nitro, cyano, C ₁ to C ₂₀ straight chain alkyl, C ₃ to C ₂₀ branched chain alkyl, cycloalkyl or aryl, wherein the cycloalkyl and the aryl Any hydrogen atom that is unsubstituted or contained is substituted by the aforementioned straight-chain alkyl group or branched-chain alkyl group. Preferably, the R ⁵ represents hydrogen, cyano, C ₁ to C ₈ linear alkyl or C ₃ to C ₇ cycloalkyl. More preferably, the R ⁵ represents hydrogen, cyano, C ₁ to C ₃ linear alkyl or C ₇ cycloalkyl.

R ⁶ represents hydrogen, C ₁ to C ₂₀ straight chain alkyl, C ₃ to C ₂₀ branched chain alkyl, C ₂ to C ₂₀ straight chain alkenyl, C ₄ to C ₂₀ branched chain alkenyl, cycloalkyl or aromatic wherein, the cycloalkyl group and the aryl group are unsubstituted or any hydrogen atom contained is substituted by the aforementioned straight-chain alkyl group, branched-chain alkyl group, straight-chain alkenyl group or branched-chain alkenyl group. Preferably, the R ⁶ represents hydrogen, C ₁ to C ₈ linear alkyl or phenyl. More preferably, the R ⁶ represents hydrogen, CH ₃ or phenyl.

Any one of -CH ₂ - contained in the groups represented by R ¹ to R ⁶ above is unsubstituted or substituted by a substituent group consisting of: -O-, -S-, -NH- , −C=O−, −O(C=O)−, −(C=O)O−, −NH(C=O)− and −(C=O)NH−, and adjacent −CH ₂ −Cannot be substituted by the above substituents at the same time. Preferably, any -CH ₂ - contained in the above-mentioned groups represented by R ¹ to R ⁶ is unsubstituted or substituted by a substituent consisting of the following groups: -C=O-, - O(C=O)− and −(C=O)O−, and adjacent −CH ₂ − cannot be substituted by the above substituents at the same time.

In the above R ¹ to R ⁶ , the cycloalkyl is unsubstituted with a carbon number range such as but not limited to 3 to 10, and the cycloalkyl is unsubstituted in a specific form such as but not limited to cyclopropyl, cyclo Butyl, cyclopentyl or cyclohexyl, etc. The carbon number of the aryl group is unsubstituted, such as but not limited to 5 to 10, and the specific aspect of the aryl group is unsubstituted, such as but not limited to phenyl, naphthyl and the like. It should also be noted that when the cycloalkyl group and the aryl group are substituted, except that any hydrogen atom contained is replaced by the aforementioned straight-chain alkyl, branched-chain alkyl, straight-chain alkenyl or branched alkenyl It can also be substituted by halogen, alkynyl, aryl, cycloalkyl or heterocyclyl.

、

、

、

、

、

、

、

、

、

、

、

、

、

或

。更佳地，該L ¹表示單鍵、C ₁至C ₃直鏈伸烷基或C ₃至C ₅支鏈伸烷基，該R ^7’表示

、

、

、

、

或

。 R ⁷ represents a bridged ring group or a derivative with a bridged ring group. Preferably, the R ⁷ represents −L ¹ −R ^7′ , wherein, the L ¹ represents a single bond, C ₁ to C ₂₀ straight chain alkylene, C ₃ to C ₂₀ branched chain alkylene or C ₄ to C ₂₀ extended (cycloalkylalkyl), the R ^7' represents

,

,

,

,

,

,

,

,

,

,

,

,

,

or

. More preferably, the L ¹ represents a single bond, C ₁ to C ₃ straight chain alkylene or C ₃ to C ₅ branched chain alkylene, and the R ^7' represents

,

,

,

,

or

.

式I-2

式I-3

式I-4

式I-5

式I-6

式I-7

式I-8

式I-9

式I-10

式I-11

式I-12

式I-13

式I-14

式I-15

Preferably, the oxime ester compound represented by formula I is one or more selected from the oxime ester compounds represented by formula I-1 to formula I-15. Formula I-1

Formula I-2

Formula I-3

Formula I-4

Formula I-5

Formula I-6

Formula I-7

Formula I-8

Formula I-9

Formula I-10

Formula I-11

Formula I-12

Formula I-13

Formula I-14

Formula I-15

。 The common preparation method of the oxime ester compound shown in the formula I is as follows, and the specific synthetic conditions can be flexibly selected and adjusted according to conventional organic synthesis methods:

.

Preferably, taking the solid content of the photosensitive resin composition as 100% by weight, the content of the oxime ester compound represented by the formula I ranges from 1% by weight to 30% by weight, so that the photosensitive resin composition has Better film-forming and curing properties; more preferably, the content range of the oxime ester compound shown in the formula I is 2% by weight to 20% by weight; most preferably, the oxime ester compound shown in the formula I The content ranges from 5% to 15% by weight.

The photosensitive resin composition of the present invention may optionally contain other reagents, such as but not limited to dispersants, pigments, solvents, coupling agents, surfactants, coatability enhancers, development improvers, ultraviolet absorbers, antioxidants, etc.

The photosensitive resin composition of the present invention can be applied in the fields of preparing photoresists for semiconductors, colored photoresists, photo spacers and other photocurable materials.

The display device of the present invention includes a colored photoresist formed from the photosensitive resin composition. The colored photoresists are, for example, black matrix photoresists and RGB color photoresists.

The semiconductor device of the present invention includes a semiconductor photoresist formed from the photosensitive resin composition.

The present invention will be further described with reference to the following examples, but it should be understood that these examples are for illustrative purposes only and should not be construed as limitations on the implementation of the present invention.

(1). 在冰浴環境中將16.7公克的咔唑與200毫升的二氯甲烷倒入一個三頸瓶中，再將33.33公克的三氯化鋁加入該三頸瓶中並攪拌30分鐘，然後將24.5公克的丁醯氯緩慢滴入該三頸瓶中且在室溫環境中反應2小時，接著在該三頸瓶中倒入冰水以中止反應，得到反應產物。將該反應產物以二氯甲烷萃取並收集有機層，接著將該有機層先以5 wt%的碳酸氫鈉水溶液酸鹼中和，再以水及飽和食鹽水洗滌，然後以無水硫酸鎂除水，最後濃縮得到粗產物。將該粗產物以管柱層析[固定相為Merck silica gel 60 (70-230 mesh ASTM)，移動相為乙酸乙酯：正庚烷＝1：4至1：2梯度沖提] 進行純化，得到18.4公克的化合物1a(產率60%)。 利用質譜儀(Perkin Elmer GC Clarus 600)分析該化合物1a的分子量，結果為MS(m/z)：307.2(M+H) ⁺。 利用核磁共振光譜儀(Bruker Avance III HD 400 MHz)分析該化合物1a的分子結構： ¹H-NMR(CDCl ₃, 400MHz)，δ(ppm)：8.772 (2H, d, J=1.2 Hz), 8.633 (1H, s), 8.141-8.117 (2H, m), 7.478 (2H, d, J=8.4 Hz), 3.084 (4H, t, J=7.2 Hz), 1.871-1.797 (4H, m), 1.054 (6H, t, J=7.6 Hz)。 (2). 在室溫環境中將30.7公克的該化合物1a、100毫升的二甲基亞碸、22.0公克的1-金剛烷基甲基丙烯酸酯(1-adamantyl methacrylate)及27.64公克的碳酸鉀加入一個反應瓶中，使該反應瓶中的混合物在50℃進行反應6小時得到反應產物。將該反應產物倒入水中，接著以乙酸乙酯萃取並收集有機層，然將該有機層先以水及飽和食鹽水洗滌，再以無水硫酸鎂除水，最後濃縮得到粗產物。將該粗產物以管柱層析[固定相為Merck silica gel 60 (70-230 mesh ASTM)，移動相為乙酸乙酯：正庚烷＝1：4]進行純化，得到26.4公克的化合物1b(產率50%)。 利用質譜儀(Thermo Scientific TSQ Altis)分析該化合物1b的分子量，結果為MS(m/z)：528.4(M+H) ⁺。 利用核磁共振光譜儀分析該化合物1b的分子結構： ¹H-NMR(CDCl ₃, 400MHz)，δ(ppm)：8.772 (2H, d, J=1.2 Hz), 8.171-8.145 (2H, m), 7.480 (2H, d, J=8.8 Hz), 4.678-4.622 (1H, m), 4.307-4.251 (1H, m), 3.098-3.010 (5H, m), 2.059 (3H, s), 1.866-1.811 (9H, m), 1.563 (5H, s), 1.233-1.166 (4H, m), 1.051 (6H, t, J=7.2 Hz)。 (3). 在冰浴環境中將52.8公克的該化合物1b、200毫升的四氫呋喃及20.3公克的濃鹽酸加到一個反應瓶中，再將29.3公克的亞硝酸異戊酯緩慢滴入該反應瓶中並在冰浴環境中進行反應，得到反應產物。將該反應產物先以飽和碳酸鉀水溶液酸鹼中和至中性，再濃縮移除四氫呋喃，接著以200毫升的乙酸乙酯萃取並收集有機層。將該有機層以水及飽和食鹽水洗滌，之後以無水硫酸鎂除水，最後濃縮得到粗產物。將該粗產物以管柱層析[固定相為Merck silica gel 60 (70-230 mesh ASTM)，移動相為乙酸乙酯：正庚烷＝1：3]進行純化，得到23.4公克的化合物1c(產率40%)。 利用質譜儀(Thermo Scientific TSQ Altis)分析該化合物1c的分子量，結果為MS(m/z)：586.4(M+H) ⁺。 利用核磁共振光譜儀分析該化合物1c的分子結構： ¹H-NMR(CDCl ₃, 400MHz)，δ(ppm)：8.954 (2H, s), 8.563 (2H, s), 8.030-8.004 (2H, m), 7.236 (2H, d, J=8.8 Hz), 4.526-4.472 (1H, m), 4.200-4.141 (1H, m), 2.990-2.900 (1H, m), 2.767 (4H, q, J=7.6 Hz), 2.115 (3H, s), 1.968 (6H, s), 1.610 (6H, s), 1.148 (6H, t, J=7.6 Hz), 1.063 (3H, d, J=6.8 Hz)。 (4). 於冰浴環境中將23.4公克的該化合物1c、80毫升的乙酸乙酯及12.3公克的醋酸酐加入一個反應瓶中並進行反應，得到反應產物。將該反應產物先以飽和碳酸鉀水溶液酸鹼中和至中性，接著以乙酸乙酯萃取並收集有機層。將該有機層以水及飽和食鹽水洗滌，之後以無水硫酸鎂除水，最後濃縮得到粗產物。將該粗產物以管柱層析[固定相為Merck silica gel 60 (70-230 mesh ASTM)，移動相為乙酸乙酯：正庚烷＝1：3]進行純化，得到18.7公克的化合物1d，即為式I-1所示的肟酯類化合物(產率70%)。 利用質譜儀(Thermo Scientific TSQ Altis)分析該化合物1d的分子量，結果為MS(m/z)：692.3(M+Na) ⁺。 利用核磁共振光譜儀分析該化合物1d的分子結構： ¹H-NMR(CDCl ₃, 400MHz)，δ(ppm)：8.915 (2H, d, J=1.2 Hz), 8.287-8.261 (2H, m), 7.510 (2H, d, J=8.8 Hz), 4.688-4.632 (1H, m), 4.303-4.247 (1H, m), 3.081-2.991 (1H, m), 2.852 (4H, q, J=7.6 Hz), 2.285 (6H, s), 2.073 (3H, s), 1.935-1.868 (6H, m), 1.574 (6H, s), 1.250-1.112 (9H, m)。 [ Example 1] The oxime ester compound shown in the formula I-1 synthesizes the oxime ester compound shown in the formula I-1 according to the following reaction pathway:

(1). Pour 16.7 grams of carbazole and 200 milliliters of dichloromethane into a three-necked bottle in an ice-bath environment, then add 33.33 grams of aluminum chloride into the three-necked bottle and stir for 30 minutes, Then 24.5 grams of butyryl chloride was slowly dropped into the three-necked bottle and reacted at room temperature for 2 hours, and then poured ice water into the three-necked bottle to stop the reaction to obtain a reaction product. The reaction product was extracted with dichloromethane and the organic layer was collected, then the organic layer was first neutralized with 5 wt% aqueous sodium bicarbonate solution, then washed with water and saturated brine, and then dehydrated with anhydrous magnesium sulfate , and finally concentrated to obtain the crude product. The crude product was purified by column chromatography [the stationary phase was Merck silica gel 60 (70-230 mesh ASTM), and the mobile phase was ethyl acetate:n-heptane=1:4 to 1:2 gradient elution], 18.4 g of compound 1a were obtained (60% yield). The molecular weight of compound 1a was analyzed by mass spectrometer (Perkin Elmer GC Clarus 600), and the result was MS (m/z): 307.2 (M+H) ⁺ . The molecular structure of the compound 1a was analyzed by nuclear magnetic resonance spectrometer (Bruker Avance III HD 400 MHz): ¹ H-NMR (CDCl ₃ , 400MHz), δ (ppm): 8.772 (2H, d, J=1.2 Hz), 8.633 ( 1H, s), 8.141-8.117 (2H, m), 7.478 (2H, d, J=8.4 Hz), 3.084 (4H, t, J=7.2 Hz), 1.871-1.797 (4H, m), 1.054 (6H , t, J=7.6 Hz). (2). At room temperature, mix 30.7 grams of the compound 1a, 100 milliliters of dimethylsulfoxide, 22.0 grams of 1-adamantyl methacrylate (1-adamantyl methacrylate) and 27.64 grams of potassium carbonate It was added to a reaction bottle, and the mixture in the reaction bottle was reacted at 50° C. for 6 hours to obtain a reaction product. The reaction product was poured into water, then extracted with ethyl acetate and the organic layer was collected, then the organic layer was washed with water and saturated brine, then dehydrated with anhydrous magnesium sulfate, and finally concentrated to obtain a crude product. The crude product was purified by column chromatography [the stationary phase was Merck silica gel 60 (70-230 mesh ASTM), and the mobile phase was ethyl acetate:n-heptane=1:4] to obtain 26.4 grams of compound 1b ( Yield 50%). The molecular weight of the compound 1b was analyzed by a mass spectrometer (Thermo Scientific TSQ Altis), and the result was MS (m/z): 528.4 (M+H) ⁺ . The molecular structure of compound 1b was analyzed by nuclear magnetic resonance spectrometer: ¹ H-NMR (CDCl ₃ , 400MHz), δ (ppm): 8.772 (2H, d, J=1.2 Hz), 8.171-8.145 (2H, m), 7.480 (2H, d, J=8.8 Hz), 4.678-4.622 (1H, m), 4.307-4.251 (1H, m), 3.098-3.010 (5H, m), 2.059 (3H, s), 1.866-1.811 (9H , m), 1.563 (5H, s), 1.233-1.166 (4H, m), 1.051 (6H, t, J=7.2 Hz). (3). Add 52.8 grams of this compound 1b, 200 milliliters of tetrahydrofuran and 20.3 grams of concentrated hydrochloric acid to a reaction flask in an ice bath environment, and then slowly drop 29.3 grams of isoamyl nitrite into the reaction flask and react in an ice-bath environment to obtain the reaction product. The reaction product was first neutralized with saturated potassium carbonate aqueous solution to acid-base to neutrality, then concentrated to remove THF, then extracted with 200 ml of ethyl acetate and the organic layer was collected. The organic layer was washed with water and saturated brine, then dehydrated with anhydrous magnesium sulfate, and finally concentrated to obtain a crude product. The crude product was purified by column chromatography [the stationary phase was Merck silica gel 60 (70-230 mesh ASTM), and the mobile phase was ethyl acetate:n-heptane=1:3] to obtain 23.4 grams of compound 1c ( Yield 40%). The molecular weight of the compound 1c was analyzed by a mass spectrometer (Thermo Scientific TSQ Altis), and the result was MS (m/z): 586.4 (M+H) ⁺ . The molecular structure of the compound 1c was analyzed by nuclear magnetic resonance spectrometer: ¹ H-NMR (CDCl ₃ , 400MHz), δ (ppm): 8.954 (2H, s), 8.563 (2H, s), 8.030-8.004 (2H, m) , 7.236 (2H, d, J=8.8 Hz), 4.526-4.472 (1H, m), 4.200-4.141 (1H, m), 2.990-2.900 (1H, m), 2.767 (4H, q, J=7.6 Hz ), 2.115 (3H, s), 1.968 (6H, s), 1.610 (6H, s), 1.148 (6H, t, J=7.6 Hz), 1.063 (3H, d, J=6.8 Hz). (4). Add 23.4 grams of the compound 1c, 80 milliliters of ethyl acetate and 12.3 grams of acetic anhydride into a reaction flask in an ice-bath environment and react to obtain a reaction product. The reaction product was first neutralized with saturated potassium carbonate aqueous solution to acidity and alkali, then extracted with ethyl acetate and the organic layer was collected. The organic layer was washed with water and saturated brine, then dehydrated with anhydrous magnesium sulfate, and finally concentrated to obtain a crude product. The crude product was purified by column chromatography [the stationary phase was Merck silica gel 60 (70-230 mesh ASTM), and the mobile phase was ethyl acetate:n-heptane=1:3] to obtain 18.7 grams of compound 1d, That is the oxime ester compound shown in formula I-1 (yield 70%). The molecular weight of the compound 1d was analyzed by a mass spectrometer (Thermo Scientific TSQ Altis), and the result was MS (m/z): 692.3 (M+Na) ⁺ . The molecular structure of compound 1d was analyzed by nuclear magnetic resonance spectrometer: ¹ H-NMR (CDCl ₃ , 400MHz), δ (ppm): 8.915 (2H, d, J=1.2 Hz), 8.287-8.261 (2H, m), 7.510 (2H, d, J=8.8 Hz), 4.688-4.632 (1H, m), 4.303-4.247 (1H, m), 3.081-2.991 (1H, m), 2.852 (4H, q, J=7.6 Hz), 2.285 (6H, s), 2.073 (3H, s), 1.935-1.868 (6H, m), 1.574 (6H, s), 1.250-1.112 (9H, m).

(購自於常州強力公司，品名TR-PBG-345)。 [ Comparative Example 1] The structure of oxime ester compound comparative example 1 oxime ester compound is as follows:

(purchased from Changzhou Qiangli Company, product name TR-PBG-345).

。 [ Comparative example 2] the structure of oxime ester compound comparative example 2 oxime ester compound is as follows:

.

The preparation method of comparative example 2 oxime ester compound is similar to the preparation method of formula I-1 oxime ester compound, the difference is that in comparative example 2, the 1-adamantyl methacrylate in step (2) is replaced into cyclohexyl acrylate.

(為專利公開號WO 2008078678A1公開的化合物No.10)。 [ Comparative example 3] the structure of oxime ester compound comparative example 3 oxime ester compound is as follows:

(Compound No.10 disclosed in Patent Publication No. WO 2008078678A1).

[ Properties Evaluation of Oxime Esters ]

Solubility:

The oxime ester compounds of embodiment 1 and comparative examples 1 to 3 were subjected to the following solubility tests respectively: in an environment of 25° C., the oxime ester compound was continuously added to 10.0 grams of propylene glycol methyl ether acetate (referred to as propylene glycol methyl ether acetate) while stirring. PGMEA) until the oxime ester compound can not be dissolved in PGMEA, record the amount of the oxime ester compound at this time as the upper limit of the dissolved amount and bring the following formula to calculate the solubility: solubility (wt%)=dissolution of the oxime ester compound The upper limit of the amount ÷ (the upper limit of the dissolved amount of oxime esters + the amount of PGMEA) × 100%.

Thermal stability:

The oxime ester compounds of Example 1 and Comparative Examples 1 to 3 were subjected to the following thermal stability tests respectively: Utilize a thermogravimetric analyzer (abbreviated as TGA, manufacturer TA instruments, model Q500), the oxime ester compounds were removed from the chamber in a nitrogen environment The temperature (25°C) was raised to 110°C, and after holding the temperature at 110°C for 30 minutes, the temperature was raised from 110°C to 400°C at a rate of 10°C/min, and the temperature at which the oxime ester compound lost 5% of its weight was recorded . Evaluation criteria for the thermal stability of oxime ester compounds are: the temperature at which 5% weight loss occurs is greater than 230°C, and the evaluation is "◎"; the temperature at which 5% weight loss occurs is 200°C to 230°C, and the evaluation is "○" ”; the temperature at which 5% weight loss occurs is less than 200°C, evaluated as “●”, and the results are recorded in Table 1.

Table 1 Solubility to PGMEA (wt%) Thermal Stability (°C) Oxime Esters Example 1 twenty one ◎ Comparative example 1 20 ● Comparative example 2 18 ● Comparative example 3 4.5 ○

Referring to the solubility results in Table 1, compared with Comparative Examples 1 to 3 oxime ester compounds, the formula I-1 oxime ester compound of embodiment 1 has a higher solubility to PGMEA, which proves that the oxime ester compound of the present invention is effective for solvents. Better solubility.

Referring to the thermal stability results in Table 1, compared with the temperature at which 5% weight loss occurred in the oxime ester compounds of Comparative Examples 1 to 3, the temperature at which the oxime ester compound of formula I-1 in Example 1 experienced a 5% weight loss Higher, it proves that the oxime ester compound of the present invention has better thermal stability. It is worth mentioning that people familiar with the technical field of photocurable materials generally recognize that the thermal stability of the photosensitive resin composition is mainly determined by the thermal stability of the photoinitiator, so the oxime ester compound of the present invention has better thermal stability. It can be seen from the stability that the photosensitive resin composition of the present invention should also have better thermal stability.

[ Application example 1] Photosensitive resin composition

Application example 1 photosensitive resin composition is to use embodiment 1 formula I-1 oxime ester compound as photoinitiator, the preparation method of application example 1 photosensitive resin composition comprises the following steps: (1). Mix 40 moles of methacrylic acid, 40 moles of benzyl methacrylate, 10 moles of hydroxyethyl methacrylate and 10 moles of acrylic acid 2-[4-(1 -Methyl-1-phenylethyl)phenoxy]ethyl ester (2-[4-(1-methyl-1-phenylethyl)phenoxy]ethyl acrylate) was copolymerized at 80°C for 5 hours to obtain base Soluble resin A (weight average molecular weight is 10000, acid value is 90 mg KOH/g). (2). With 60 grams of epoxy compound (manufacturer: DIC company, model: N740, epoxy equivalent: 181 grams/equivalent), 15 grams of acrylic acid, 200 grams of PGMEA, 2.5 grams of 1-methylimidazole and 0.15 grams of p-methoxyphenol was reacted at 100° C. for 10 hours to obtain an epoxy acrylate solution (acid value is below 5 mgKOH/g). Afterwards, the epoxy acrylate solution of 25 parts by weight and the tetrahydrophthalic anhydride (THPA) of 2.5 parts by weight were reacted for 4 hours at 80 DEG C to obtain alkali-soluble resin B (the weight-average molecular weight is 8000, and the acid value is 100 mg KOH/g). (3). The alkali-soluble resin B of 25 parts by weight, the alkali-soluble resin A of 6 parts by weight, the dipentaerythritol hexaacrylate of 30 parts by weight, the oxime ester of the embodiment 1 formula I-1 of 6 parts by weight Compounds, 260 parts by weight of black pigment and 500 parts by weight of solvent (made up of 100 parts by weight of 3-ethoxy ethyl propionate and 400 parts by weight of PGMEA) are uniformly mixed to obtain the photosensitive material of Application Example 1. Resin composition.

[ Reference example 1 to 2] Photosensitive resin composition

(購自於常州強力公司，型號TR-PBG-314) 參考例2

(購自於常州強力公司，型號TR-PBG-358) The difference between the photosensitive resin compositions of Reference Examples 1 and 2 and Example 1 is that Reference Examples 1 and 2 respectively use the following oxime ester compounds as photoinitiators: Photoinitiator Reference example 1

(purchased from Changzhou Qiangli Company, model TR-PBG-314) Reference example 2

(purchased from Changzhou Qiangli Company, model TR-PBG-358)

[ Property Evaluation of Photosensitive Resin Composition ]

Mura Defect detection:

The photosensitive resin compositions of Application Example 1 and Reference Examples 1 to 2 were respectively subjected to the following mura defect detection: the photosensitive resin composition was coated on the substrate and then dried at 100°C for 1 minute to form a coating film with a thickness of 1.5 μm. After the coating film was cooled to room temperature, the coating film was exposed by I-line, and then the exposed coating film was developed at 24°C for 40 seconds using a KOH aqueous solution with a concentration of 1 wt% to form a patterned coating film , and then high-pressure cleaning the patterned coating film by using a high-pressure jet cleaning machine for 30 seconds, and then hard-baking at 230° C. for 20 minutes to form a black photoresist. Under yellow light, the mura defects of the black photoresist were visually inspected.

Table 2 Detection of mura defects in black photoresists Photosensitive resin composition Application example 1 Virtually invisible mura defects Reference example 1 with black line Reference example 2 with black line

Referring to Table 2, compared with mura defects in the black photoresists formed by the photosensitive resin compositions of Reference Examples 1 and 2, mura defects are almost invisible in the black photoresist formed by the photosensitive resin composition of Application Example 1, proving that The photosensitive resin composition of the present invention has better film-forming properties, developing properties and photosensitivity.

But what is described above is only an embodiment of the present invention, and should not limit the scope of the present invention. All simple equivalent changes and modifications made according to the patent scope of the present invention and the content of the patent specification are still within the scope of the present invention. Within the scope covered by the patent of the present invention.

none.

Claims (16)

A photosensitive resin composition, comprising: an alkali-soluble resin; a polymerizable monomer, different from the alkali-soluble resin; and a photoinitiator, including at least one oxime ester compound represented by formula I: [formula I ]

In this formula I, R ¹ to R ⁴ each independently represent C ₁ to C ₂₀ straight chain alkyl, C ₃ to C ₂₀ branched chain alkyl, C ₂ to C ₂₀ straight chain alkenyl, C ₄ to C ₂₀ branched Alkenyl, cycloalkyl or aryl, wherein, the cycloalkyl and the aryl are unsubstituted or any hydrogen atom contained is substituted by the aforementioned alkyl or alkenyl, R ⁵ represents hydrogen, halogen, nitrate group, cyano group, C ₁ to C ₂₀ linear alkyl group, C ₃ to C ₂₀ branched chain alkyl group, cycloalkyl group or aryl group, wherein the cycloalkyl group and the aryl group are unsubstituted or contained Any hydrogen atom is substituted by the aforementioned alkyl group, R ⁶ represents hydrogen, C ₁ to C ₂₀ straight chain alkyl, C ₃ to C ₂₀ branched chain alkyl, C ₂ to C ₂₀ straight chain alkenyl, C ₄ to C ₂₀ Branched alkenyl, cycloalkyl or aryl, wherein, the cycloalkyl and aryl are unsubstituted or any hydrogen atom contained is substituted by the aforementioned alkyl or alkenyl, the above R ¹ to R ⁶ represent Any −CH ₂ − contained in the group is unsubstituted or substituted by a substituent consisting of the following groups: −O−, −S−, −NH−, −C=O−, −O(C=O)−, −(C=O)O−, −NH(C=O)− and −(C=O)NH−, and adjacent −CH ₂ − cannot be replaced by the above at the same time Substituted by a group, and R ⁷ represents a bridged ring group or a derivative of a bridged ring group. The photosensitive resin composition as claimed in item 1, wherein, in the formula I, the R ⁷ represents −L ¹ −R ^7' , wherein, the L ¹ represents a single bond, C ₁ to C ₂₀ straight chain alkane group, C ₃ to C ₂₀ branched alkylene or C ₄ to C ₂₀ extended (cycloalkylalkyl), the R ^7' represents

,

,

,

,

,

,

,

,

,

,

,

,

,

or

. The photosensitive resin composition as claimed in item 2, wherein, in the formula I, the L ¹ represents a single bond, a C ₁ to C ₃ straight chain alkylene or a C ₃ to C ₅ branched chain alkylene, the R ^7' means

,

,

,

,

or

. The photosensitive resin composition as claimed in item 1, wherein, in the formula I, the R ¹ to R ⁴ each independently represent a C ₁ to C ₈ linear alkyl group, a C ₃ to C ₁₀ branched chain alkyl group or C ₃ to C ₆ cycloalkyl, R ⁵ represents hydrogen, cyano, C ₁ to C ₈ linear alkyl or C ₃ to C ₇ cycloalkyl, and R ⁶ represents hydrogen, C ₁ to C ₈ linear alkane group or phenyl group, and any -CH ₂ - contained in the groups represented by R ¹ to R ⁶ above is unsubstituted or substituted by a substituent group consisting of: -C=O−, −O(C=O)− and −(C=O)O−, and adjacent −CH ₂ − cannot be substituted by the above substituents at the same time. The photosensitive resin composition as claimed in item 4, wherein, in the formula I, R ¹ and R ² each independently represent a C ₁ to C ₂ linear alkyl group, and R ³ and R ⁴ each independently represent a C ₁ to C ₅ straight chain alkyl or C ₃ to C ₁₀ branched chain alkyl, R ⁵ represents hydrogen, cyano, C ₁ to C ₃ straight chain alkyl or C ₇ cycloalkyl, R ⁶ represents hydrogen, CH ₃ or phenyl. The photosensitive resin composition according to claim 1, wherein the content of the oxime ester compound ranges from 1% to 30% by weight, taking the solid content of the photosensitive resin composition as 100% by weight. The photosensitive resin composition as described in claim 1, wherein, taking the solid content of the photosensitive resin composition as 100% by weight, the content of the alkali-soluble resin ranges from 5% to 60% by weight. The photosensitive resin composition as described in claim 1, wherein, taking the solid content of the photosensitive resin composition as 100% by weight, the content of the polymerizable monomer ranges from 5% to 60% by weight. A kind of oxime ester compound, is represented by formula I: [formula I]

In the formula I, R ¹ to R ⁴ each independently represent C ₁ to C ₂₀ straight chain alkyl, C ₃ to C ₂₀ branched chain alkyl, C ₄ to C ₂₀ cycloalkyl alkyl, C ₂ to C ₂₀ Straight chain alkenyl, C ₄ to C ₂₀ branched alkenyl, cycloalkyl or aryl, wherein, the cycloalkyl and the aryl are unsubstituted or any hydrogen atom contained is replaced by the aforementioned alkyl or alkenyl ^R represents hydrogen, halogen, nitro, cyano, C ₁ to C ₂₀ straight chain alkyl, C ₃ to C ₂₀ branched chain alkyl, cycloalkyl or aryl, wherein, the cycloalkyl and The aryl group is unsubstituted or any hydrogen atom contained is substituted by the above-mentioned alkyl group; R ⁶ represents hydrogen, C ₁ to C ₂₀ straight chain alkyl, C ₃ to C ₂₀ branched chain alkyl, C ₂ to C ₂₀ straight-chain alkenyl, C ₄ to C ₂₀ branched alkenyl, cycloalkyl or aryl, wherein, the cycloalkyl and the aryl are unsubstituted or any hydrogen atom contained is replaced by the aforementioned alkyl or Alkenyl substitution; any -CH ₂ - contained in the groups represented by the above R ¹ to R ⁶ is unsubstituted or substituted by a substituent consisting of the following groups: -O-, -S- , −NH−, −C=O−, −O(C=O)−, −(C=O)O−, −NH(C=O)− and −(C=O)NH−, and adjacent The −CH ₂ − in is not allowed to be substituted by the above substituents at the same time; and R ⁷ represents a bridged ring group or a derivative with a bridged ring group. The oxime ester compound as described in claim item 9, wherein, in the formula I, the R ⁷ represents −L ¹ −R ^7' , wherein, the L ¹ represents a single bond, C ₁ to C ₂₀ straight-chain alkylene , C ₃ to C ₂₀ branched alkylene or C ₄ to C ₂₀ extended (cycloalkylalkyl), the R ^7' represents

,

,

,

,

,

,

,

,

,

,

,

,

,

or

. The oxime ester compound as described in claim item 10, wherein, in the formula I, the ^L represents a single bond, C ₁ to C ₃ straight chain alkylene or C ₃ to C ₅ branched chain alkylene, and the R ^7' means

,

,

,

,

or

. The oxime ester compound as described in claim item 9, wherein, in the formula I, the R ¹ to R ⁴ each independently represent C ₁ to C ₈ straight-chain alkyl, C ₃ to C ₁₀ branched-chain alkyl or C ₃ to C ₆ cycloalkyl, R ⁵ represents hydrogen, cyano, C ₁ to C ₈ linear alkyl or C ₃ to C ₇ cycloalkyl, and R ⁶ represents hydrogen, C ₁ to C ₈ linear alkyl or phenyl, and any -CH ₂ - contained in the groups represented by R ¹ to R ⁶ above is unsubstituted or substituted by a substituent group consisting of: -C=O-, - O(C=O)− and −(C=O)O−, and adjacent −CH ₂ − cannot be substituted by the above substituents at the same time. The photosensitive resin composition according to claim 12, wherein, in the formula I, R ¹ and R ² each independently represent a C ₁ to C ₂ linear alkyl group, and R ³ and R ⁴ each independently represent a C ₁ to C ₅ straight chain alkyl or C ₃ to C ₁₀ branched chain alkyl, R ⁵ represents hydrogen, cyano, C ₁ to C ₃ straight chain alkyl or C ₇ cycloalkyl, R ⁶ represents hydrogen, CH ₃ or phenyl. A use of the photosensitive resin composition according to any one of Claims 1 to 8, including the application in the preparation of photo-spacers, colored photoresists or photoresists for semiconductors. A display device comprising a colored photoresist formed of the photosensitive resin composition according to any one of Claims 1 to 8. A semiconductor device, comprising a semiconductor photoresist formed of the photosensitive resin composition according to any one of claims 1 to 8.